CN101133113B - Use of a specific platinum compound in order to improve the resistance of silicon elastomers to degradation caused by very high temperatures - Google Patents
Use of a specific platinum compound in order to improve the resistance of silicon elastomers to degradation caused by very high temperatures Download PDFInfo
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- CN101133113B CN101133113B CN2006800071161A CN200680007116A CN101133113B CN 101133113 B CN101133113 B CN 101133113B CN 2006800071161 A CN2006800071161 A CN 2006800071161A CN 200680007116 A CN200680007116 A CN 200680007116A CN 101133113 B CN101133113 B CN 101133113B
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 18
- 230000015556 catabolic process Effects 0.000 title claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 6
- 150000003058 platinum compounds Chemical class 0.000 title abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 119
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 59
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 18
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- 239000002253 acid Substances 0.000 claims abstract description 8
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- 239000000203 mixture Substances 0.000 claims description 114
- 125000000217 alkyl group Chemical group 0.000 claims description 100
- -1 propylene, butylene, tetrahydrobenzene Chemical class 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 45
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000000470 constituent Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 19
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- 125000000962 organic group Chemical group 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
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- 239000000376 reactant Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
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- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
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- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
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- 239000000126 substance Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- 229910019032 PtCl2 Inorganic materials 0.000 abstract 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
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- 239000003513 alkali Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
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- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
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- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 1
- FXNONNRUNQPNLF-UHFFFAOYSA-N cerium;2-ethylhexanoic acid Chemical compound [Ce].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O FXNONNRUNQPNLF-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
The purpose of the present invention is to demonstrate that silicon elastomers originating from RTV-, LSR-, polyaddition EVC- or EVC-type polyorganosiloxane compounds undergo significantly-less degradation as a result of very high temperatures when at least one specific platinum compound that complies with the definition below is used as a stabilising additive. Said compound is selected from the group comprising: a) at least one platinum complex selected from among products having formula (I.1), wherein A, B, T1, T2, T3, T4, Rc and Rd are as defined in claim 1; and b) a combination of a) with at least one other platinum complex such as hexachloroplatinic acid and the derivatives thereof, complexes having formula (PtCl2, olefin)2 and the complexes of platinum and vinyl organopolysiloxanes. The use of articles that are made from stabilised silicon elastomers in accordance with the invention is advantageous in the electrical engineering field.
Description
Technical field
The present invention relates at least a specific platinic compound in being intended to obtain the constituent polyorganosiloxane composition of silicone elastomer as the purposes that can improve the stabilising additive of degradation property under the effect of silicone elastomer superhigh temperature resistant, wherein said composition at high temperature crosslinked under the organo-peroxide effect (being known as the composition of HCR or HCE) or by the polyaddition in the presence of metal catalyst crosslinked at ambient temperature or heat cross-linking (being known as RTV, the composition of LSR or poly-addition HCE).
Background technology
Term RTV, LSR and HCE well known to a person skilled in the art: RTV is the abbreviation of " self cure "; LSR is the abbreviation of " liquid silicone rubber ", and HCR is the abbreviation of " thermofixation rubber ", and HCE is the abbreviation of " thermal curable elastomerics ".
In electrical technology field, above-mentioned constituent polyorganosiloxane composition for example can be used for producing first strip of paper used for sealing or the insulating material that uses when forming fire-resistant wires or cable.
Term " fire-resistant wires or cable " is meant and should guarantees at least at the electric wire or the cable that have the high quality fire performance aspect ash content cohesiveness (coh é sion des cendres) and the cigarette opacity.Fire-resistant wires or cable the characteristic that should have constituted the theme of rules in many countries, and drafted strict standard.
For example in France, the major criterion relevant with the fire testing of cable (it is desirable satisfying this standard) is standard NF C 32-070 CR1, and it relates to the run duration of incendiary cable under specified requirements.Resistivity against fire is to the generation of small part owing to ash content, and this ash content should have certain cohesiveness so that can keep the enough insulativity of the work of cable.In this test, each cable sample is placed metal tube, subsequently metal tube itself is placed stove, furnace temperature reached 920 ℃ in 50 minutes, kept 15 minutes in this value subsequently; In this process of the test, cable sample is subjected to the impact (by means of impacting rod, its speed with twice/minute impacts metal tube) of dried rule; Do not extinguish as yet if the control lamp that links to each other with the cable that is subjected to rated voltage (that is to say, after 65 minutes) when duration of test runs finishes, then this test is successful; If the success of the test of at least 80 quantity % that implemented then meets this standard.
According to known prior art, cable is made of one or more uniconductors (usually based on Cu or based on A1); Each uniconductor in these uniconductors is by first strip of paper used for sealing or insulating material protection, and this first strip of paper used for sealing or insulating material are made by one or more layers concentric layer based on silicone elastomer.Provide especially based on glass fibre and/or based on one or more packing elements and/or one or more enhancing element of mineral fibre around this strip of paper used for sealing or these strips of paper used for sealing (under the situation of the cable that comprises several uniconductors).Cable carries out outer the coating subsequently, and it can comprise one or more sheaths.
Under the situation of the cable that comprises several uniconductors, be positioned at uniconductor (each uniconductor has its first insulating material) on every side packing elements and/or strengthen element constituted combination uniconductor shared strip of paper used for sealing.Although the silicone elastomer that uses when forming cable is the constituent material of first insulating material basically, it can also be present in variable ratio: in packing elements and/or the enhancing element (constituting shared strip of paper used for sealing under the situation of the cable that comprises several uniconductors); And/or in the oversheath.
In electrical technology field, above-mentioned constituent polyorganosiloxane composition can also be used in and for example can adopt in the elastomeric any application of organopolysiloxane, and this organopolysiloxane elastomerics not only is difficult to burning, but also anti-current and electric arc are revealed; This constituent polyorganosiloxane composition can be used in particular for producing the anode cap of electrically insulating material, medium and high pressure isolator, cable terminal end accessory, cable splice, teletube and moulded product or the extruded product that aircraft industry is used.
In this respect, another major criterion relevant with fire testing (it also is desirable satisfying this standard) is international standard IEC 60587 (IEC is the abbreviation of International Electrotechnical Commission), and it relates to measures the anti-electric trace index of solid insulating material when standing the harsh temperatures condition; Anti-electric trace index combines with the mensuration of when needed erosion value, is used as standard for acceptance and as the standard of the quality of the control material of producing.
Platinum is at the positive effect aspect the decomposition of silicone elastomer and celebrated stabilising additive with it.
Know platinum and the formula (FeO) used by JP-A-76/035 501
x(Fe
2O
3)
yMix the mixture of ferriferous oxide, wherein ratio x/y is 0.05/1 to 1/1, thereby improves the flame retardant resistance of the silicone elastomer that is obtained by the HCE composition.
Know mixture, particularly platinum and cerium (IV) the oxide compound CeO that uses platinum and at least a rare-earth oxide by FR-A-2 166 313 and EP-A-0 347 349
2Mixture, thereby improve the flame retardant resistance of the silicone elastomer that obtains by HCE composition (FR-A-2 166 313) or RTV composition (EP-A-0 347349).
Also know by EP-A-0 951 503, also can improve the anti-electric trace and the arc resistance of silicone elastomer by use based on the mixture of the compound of platinum and the transition metal except that platinum.
The related platinum of prior art can be especially:
-platinum (element) form, or
-following form:
● Platinic chloride H
2PtCl
66H
2O (described in patent US-A-2 823 218),
● anhydrous Platinic chloride,
●PtCl
2[P(CH
2-CH
2-CH
3)
3]
2,
● title complex, for example formula (PtCl described in the patent US-A-3 159 601
2Alkene)
2Those, the alkene in this title complex is meant ethene, propylene, butylene, tetrahydrobenzene or vinylbenzene especially,
● (PtCl
2C
3H
6)
2, the title complex of platinum chloride described in U.S. Pat-A-3 159 662 and chloropropane,
● the title complex of platinum and vinylated organopolysiloxane, for example Karstedt catalyzer (referring to US-A-3 775 452).
Anhydrous Platinic chloride and Karstedt catalyzer are the examples of particularly suitable platinum stablizer.
Summary of the invention
Applicant company has been found that (and this discovery has constituted theme of the present invention) now, if use at least a and the corresponding specific platinic compound of definition that hereinafter provides in the present invention as stabilising additive, then reduced the decomposition of the silicone elastomer that obtains by RTV, LSR, poly-addition HCE or HCE type constituent polyorganosiloxane composition really.
More specifically, the present invention therefore relate to platinum in being intended to obtain the constituent polyorganosiloxane composition C of silicone elastomer as the purposes that can improve the stabilising additive of degradation property under the effect of silicone elastomer superhigh temperature resistant, said composition at high temperature crosslinked or crosslinked at ambient temperature or heat cross-linking of polyaddition by in the presence of metal catalyst under the organo-peroxide effect wherein, described purposes is characterised in that platinum is at least a form that is selected from following compound:
A): at least a platinum complex that is selected from the product of formula (I):
Wherein:
Wherein:
A and B represent C or N independently, it should be understood that when A represents N T
4Without any implication, when B represents N, T
3Without any implication;
T
3And T
4Represent hydrogen atom independently; Alkyl; Optional by the cycloalkyl of alkyl or alkoxyl group replacement; Optional by the aryl of alkyl or alkoxyl group replacement; Thiazolinyl; Alkynyl; Or arylalkyl, wherein aryl moiety is optional is replaced by alkyl or alkoxyl group; Perhaps
T
1And T
2Represent alkyl independently; The optional alkyl that is replaced by alkyl; Perfluorinated alkyl or the optional alkyl that is replaced by perfluoroalkyl; Optional by the cycloalkyl of alkyl or alkoxyl group replacement; Optional by the aryl of alkyl or alkoxyl group replacement; Thiazolinyl; Alkynyl; Or arylalkyl, wherein aryl moiety is optional is replaced by alkyl or alkoxyl group; Perhaps
V
1-V
2 (V)
Wherein:
● V
1Be bivalent hydrocarbon radical, preferred alkylidene group,
● V
2Be to be selected from following substituent monoradical:
◆ alkoxyl group ,-OR °, wherein R ° corresponding to alkyl or aryl,
◆ amine, preferred N (R °)
2, wherein R ° corresponding to hydrogen, alkyl or aryl,
T
1And T
2Represent the monoradical of following formula (W) independently:
W
1-ω-W
2 (W)
Wherein:
● W
1Be bivalent hydrocarbon radical, preferred straight chain or branching C
1-C
10Alkylidene group, it randomly is substituted,
● the ω representative:
-R
1C=CR
1-
R wherein
1Corresponding to H or alkyl, perhaps
-C≡C-
● W
2Be to be selected from following substituent monoradical:
R wherein
5=alkyl;
R wherein
6=alkyl;
R wherein
7=H or alkyl;
R wherein
8=alkyl;
Perhaps, substituting group T
1, T
2, T
3And T
4Can form saturated in twos or aliphatic unsaturated hydrocarbon when being arranged in when two adjacent ring members of formula (II) go up;
L
αAnd L
βBe the part that is same to each other or different to each other, and
→ representative separately:
Wherein, in these formulas (III.1) with (III.2):
Z
1, Z
2, Z
3, Z
4, Z
5And Z
6
● representative independently of one another:
A. hydrogen,
B. halogen,
C. cyano group,
D. saturated or unsaturated electrophilic alkyl, preferably adjacent with two keys or triple bond,
E. two adjacent Z
1To Z
6Can form advantageously Cabbeen L together with formula (II)
γDifferent and the optional electrophilic ring that comprises heteroatoms (preferred O, N or S);
● perhaps, substituting group Z
1And Z
2Form the unit price thiazolinyl together in (III.1), this unit price thiazolinyl comprises at least one preferably adjacent with triple bond electrophilic residue,
● perhaps, Z
3To Z
6Form the unit price thiazolinyl in (III.2) in twos, this unit price thiazolinyl comprises at least one preferably adjacent with two keys electrophilic residue;
→ or form the ligand L of formula (IV) together
δ:
Wherein:
X represents O, NR
eOr CR
fR
g
R
10, R
11, R
13And R
14Identical or different, be selected from hydrogen atom, alkyl or the optional aryl that is replaced by alkyl;
R
9, R
12, R
a, R
bAnd R
eBe independently selected from hydrogen atom; Alkyl; Acyl group; The optional aryl that is replaced by alkyl; The optional cycloalkyl that is replaced by alkyl; And arylalkyl, wherein aryl moiety is optional is replaced by alkyl;
R
cAnd R
dBe independently selected from alkyl; The optional aryl that is replaced by alkyl; The optional cycloalkyl that is replaced by alkyl; And arylalkyl, wherein aryl moiety is optional is replaced by alkyl; Perhaps
Work as Y
1And Y
2Represent SiR independently
cR
dThe time, be bonded to two R on two differences (distinct) Siliciumatom
cGroup forms the chain of following formula together:
Wherein n is 1 to 5 integer; X as above defines; R and R ' are identical or different, have as above at R
cOr R
dIn the implication that provides any one;
Perhaps
Work as Y
1And Y
2Represent SiR independently
cR
dThe time, be bonded to two R on the Different Silicon atom
cGroup forms saturated hydrocarbon chain together, these two R
cGroup forms 6-to 10-unit ring with described Siliciumatom and X; Perhaps
Work as Y
1And Y
2Represent CR independently
aR
bThe time, be bonded to two R on the different carbon atoms
aGroup forms saturated hydrocarbon chain together, these two R
aGroup forms 6-to 10-unit ring with carbon atom that carries them and X; And
R
fAnd R
gRepresent hydrogen atom independently of one another; Alkyl; Acyl group; The optional aryl that is replaced by alkyl; The optional cycloalkyl that is replaced by alkyl; Arylalkyl, wherein aryl moiety is optional is replaced by alkyl; Halogen atom; Thiazolinyl; Alkynyl; Or SiG
1G
2G
3Group, wherein G
1, G
2And G
3Be alkyl independently of one another; Alkoxyl group; Optional by the aryl of alkyl or alkoxyl group replacement; Or arylalkyl, wherein aryl moiety is optional is replaced by alkyl or alkoxyl group;
B): (a) with the combination of at least a other platinum complex, this at least a other platinum complex is selected from: the title complex of 0 oxidation state platinum, the title complex of+2 oxidation state platinum or+title complex of 4 oxidation state platinum.
The composition C that comprises in addition according to stabilising additive of the present invention solidifies the generation elastomerics, the situation of appearance is compared during with the platinum based stabilizer (the particularly wherein the most effective platinum based stabilizer of being made up of Karstedt platinum and anhydrous Platinic chloride) that uses prior art, and the degraded of this elastomerics under the ultra high temp effect is much lower.
Term " ultra high temp " is understood that to be meant especially and is higher than 500 ℃, preferably is higher than 800 ℃ temperature.When the residence time in the temperature that for example is higher than 200 ℃ even 250 ℃ is extended, for example surpass 200 hours, preferably surpass 240 hours, then especially these temperature can be considered as ultra high temp.
Specific platinic compound
Platinum complex definition a) of following compensation type (I).
Term " alkyl " is meant saturated optional replacement (for example being replaced by one or more alkyl) straight chain or branching hydrocarbon chain, preferably contains 1 to 10 carbon atom, for example 1 to 8 carbon atom, more preferably 1 to 7 carbon atom.
The example of alkyl is methyl, ethyl, sec.-propyl, n-propyl, the tertiary butyl, isobutyl-, normal-butyl, n-pentyl, isopentyl and 1 particularly, the 1-dimethyl propyl.
The moieties of alkoxyl group as above defines.
Term " cycloalkyl " is considered to be meant saturated list-or many rings, preferred single-or dicyclo alkyl, preferably have 3 to 10 carbon atoms, better 3 to 8 carbon atoms.Term " saturated multi-ring alkyl " is considered to be meant that having two or more is connected to each other via the σ key and/or the group of condensed ring nucleus in twos.
The example of polycyclic cycloalkyl is diamantane and norbornane.
The example of monocyclic cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.
Term " perfluorinated alkyl " is meant the alkyl that comprises at least one perfluoroalkyl, preferably has following formula:
-(CH
2)
p-C
qF
2q+1
Wherein p represents 0,1,2,3 or 4; Q is 1 to 10 integer; C
qF
2q+1Be straight chain or branching.The preferred example of this group is :-(CH
2)
2-(CF
2)
5-CF
3With-(CF
2)
7-CF
3
Term " aryl " is meant the monocycle or the polycyclic of the aromatics that contains 6 to 18 carbon atoms, the alkyl of preferred monocycle or dicyclo.It should be understood that in the present invention term " the many cyclic groups of aromatics " is considered to be meant that such group, this group have two or more virtue that condenses (ortho-condensed or ortho position and peri-condensed) each other nuclear, also promptly has at least two total carbon in twos.
Described aromatic hydrocarbon radical (" aryl ") is randomly for example by one or more C
1-C
3Alkyl, one or more halo alkyl (CF for example
3), one or more alkoxyl groups (CH for example
3O) or one or more one or more ketone unit (CH for example that comprises
3CO-) alkyl replaces.
As the example of aryl, can mention phenyl, naphthyl, anthryl and phenanthryl.
Term " arylalkyl " is meant the alkyl as defined above that is replaced by one or more aryl on its hydrocarbon chain, this aryl as above defines.Its example is benzyl and trityl group.
Term " acyl group " is considered to be meant R °-CO-group, and wherein R ° is meant alkyl as defined above; Or the Ar-CO-group, wherein Ar is meant aryl as defined above, perhaps arylalkyl, and wherein " aryl " and " alkyl " as above defines, and wherein aryl moiety is optional is replaced by for example alkyl.
Term " thiazolinyl " is considered to be meant undersaturated replacement or unsubstituted straight chain or the branching hydrocarbon chain with at least one olefinic double bond and more preferably single pair key.Preferably, this thiazolinyl has 2 to 8 carbon atoms, better 2 to 6 carbon atoms.Optional at least one heteroatoms, for example O, N or the S of comprising of this hydrocarbon chain.
The preferred example of this thiazolinyl is allyl group and high allyl.
According to the present invention, term " alkynyl " is considered to be meant to have at least one acetylene series triple bond and the undersaturated replacement of more preferably single triple-linked or unsubstituted straight chain or branching hydrocarbon chain.Preferably, this alkynyl has 2 to 8 carbon atoms, better 2 to 6 carbon atoms.As an example, can mention ethynyl and propargyl.Optional at least one heteroatoms, for example O, N or the S of comprising of this hydrocarbon chain.
Term " without any implication " is meant substituting group-T
3With-T
4Do not exist respectively.This be because, in formula (II), nitrogen-atoms is tervalent, therefore when A or B represented N, nitrogen-atoms can not have other substituting group.
Preferably, in the carbenes of formula (II):
Be preferably following groups: methyl, n-propyl, n-pentyl, neo-pentyl (CH
2-C (CH
3)
3), cyclopentyl, cyclohexyl, adamantyl, allyl group (CH
2-CH=CH
2), methylallyl (CH
2-C (CH
3)=CH
2), propargyl, high-propargyl ((CH
2)
2-C ≡ CH),
Perhaps
Perhaps
Perhaps :-(CH
2)
γ=1 is to 4-amine (N (CH for example
3)
2) or-(CH
2)
γ=1 is to 4-alkoxyl group (O (CH for example
3)
2);
According to another alternative form, with ligand L
γThe Cabbeen of corresponding formula (II) can have at least two and condense nuclear, that is to say, at least from being positioned at two T on the adjacent ring member
1, T
2, T
3And T
4Two substituting groups form the saturated or aliphatic unsaturated hydrocarbon that preferably has 3 to 6 carbon atoms together.Term " saturated or aliphatic unsaturated hydrocarbon " is considered to be meant the linearity or the branching hydrocarbon chain of the degree of unsaturation that can have or can not have one or more olefinic double bonds or acetylene series three key types.
Condense when nuclear when Cabbeen (II) has two, thereby they are corresponding to one of following formula, wherein saturated the or aliphatic unsaturated hydrocarbon of (alk) representative:
The ligand L of formula (I)
αAnd L
βProduct can be represented independently by group Z
1To Z
6The alkynyl of the formula (III.1) that replaces or the thiazolinyl of formula (III.2), this group Z
1To Z
6Have at least one at L
αAnd L
βπ-degree of unsaturation aspect be active to promote the coordinate electrophilic unit with the platinum of title complex.
Advantageously, in formula (III.1) with (III.2), the electrophilic residue is selected from:
Wherein: R
17, R
18, R
19Or R
20Be replacement or unsubstituted alkyl, thiazolinyl, alkynyl or trialkylsilkl, n ' is 1 to 50.
As group Z
1To Z
6Example, can mention:
-CN ,-COOCH
3,-COOCH
2CH
3,-CONC
12H
25With-COO-CH
2-CH=CH
2,
And substituting group Z therein
1And Z
2Two two places and in (III.1), form ring Cy1 and Z wherein with triple bond
3To Z
6Two two places with or in (III.2), does not form under the situation of encircling Cy2 with two keys, these encircle Cy1 and Cy2 is selected from following ring independently and preferably:
Work as L
αAnd L
βForm the ligand L of formula (IV) together
δThe time, the latter is preferably wherein Y
1And Y
2All represent CR
dR
bAll represent SiR
cR
dThe part of type, make described title complex for formula (IV.1) or be the title complex of formula (IV.2):
Wherein:
Two R
aGroup, two R
bGroup, two R
cGroup and two R
dGroup is mutually the same, and R
9=R
12R
10=R
14And R
11=R
13
According to a kind of alternative form, (IV.2) two R in
cGroup forms together:
(a) chain
Wherein n is 1 to 5 integer; X as above defines; And R and R ' are identical or different, have as above at R
cOr R
dIn the given implication any one;
(b) or saturated hydrocarbon chain, so that two substituent R
cForm 6-to 10-unit ring with two Siliciumatoms that carry them and X, preferred 6-to 8-unit ring.
As two R
cWhen group formed chain (a) in (IV.2), n preferably had 1 or 2 value and R=R
d, two R that carry by two Siliciumatoms
dGroup is identical.In this case, R
dPreferred alkyl, for example methyl represented.Better, in these compounds, R ' representative-CR
12=CR
13R
14R
13=R
11R
10=R
14And R
12=R
9
In this case, the X in (IV.2) preferably represents O.Ligand L
δThen have following formula:
In the middle of these compounds, two R
dGroup is preferred identical and advantageously represent alkyl (for example methyl).
Preferably, n has 1 or 2 value and R=R
d, it should be understood that when n has value 2, O-(SiRR '-O)
nOnly Siliciumatom of-chain can be replaced by one or two alkenyl or alkynyl.Better, R '=-CR
12=CR
13R
14And R
13=R
11R
10=R
14And R
12=R
9
As two R
cWhen group forms chain (b) with two Siliciumatoms and radicals X, two R
cGroup is preferably 8-unit ring.In this case, two R
dGroup is preferably identical.Ligand L
δThen have following formula:
Wherein T represents alkyl, and i is 0 to 5 integer, and T is positioned on 1,2,3,4 and 5 ring members one or more of following formula.
Similarly, work as Y
1And Y
2CR in the representative (IV.1)
aR
bThe time, be bonded to two R on the different carbon atoms
aGroup can form saturated hydrocarbon chain (c) together so that two R
aGroup forms 6-to 10-unit ring with carbon that carries them and X.Preferably, the ring of formation is 8-unit ring, ligand L in this case
δThen have following formula:
Wherein T represents alkyl; I is 0 to 5 integer, and T is positioned on 1,2,3,4 and 5 ring members one or more of following formula.
Work as R
fAnd/or R
gRepresent SiG
1G
2G
3The time, R
fAnd/or R
gBe preferably trialkylsilkl, for example G
1=G
2=G
3SiG during=alkyl
1G
2G
3
Contained ligands for metal complexes L in the present composition
δSubclass constitute by following this class title complex, for this class title complex:
-X=O; Y
1And Y
2Represent SiR independently
cR
dOr
-X=NR
eY
1And Y
2Represent CR independently
aR
bOr
-X=NR
eY
1And Y
2Represent SiR independently
cR
dOr
-X=CR
fR
gY
1And Y
2Represent CR independently
aR
bOr
-X=CR
fR
gY
1And Y
2Represent SiR independently
cR
d
These ligand L in formula (IV)
δIn the middle of, preferably following these, for these parts:
-when X represents O, Y
1And Y
2Represent SiR independently
cR
dOr
-represent NR as X
eThe time, Y
1And Y
2Represent CR independently
aR
bOr
-represent CR as X
fR
gThe time; Y
1And Y
2Represent CR independently
aR
b
In the practice, X represents O and Y
1And Y
2Represent the ligand L of formula (IV) independently
δIn SiR
cR
d
In the present invention, term " representative " the independently meaning is that the substituting group of indication is identical or is different.
For example, in the ligand L of formula (IV)
δIn, R
10, R
11, R
13And R
14It is hydrogen atom.
R
9And R
12Preferred meaning hydrogen atom particularly; Alkyl; The optional aryl that is replaced by alkyl; With the optional cycloalkyl that is replaced by alkyl.In the middle of these preferred implications, identical R
9And R
12Particularly advantageously represent hydrogen atom; (C
3-C
8) cycloalkyl or (C
1-C
8) alkyl.
For example, the diolefinic ligand L of formula (IV)
δBe symmetric, that is to say, R
10=R
14R
11=R
13R
9=R
12, and two group Y
1And Y
2Be: otherwise identical from one another, or Y
1=CR
aR
bAnd Y
2=CR
aR
b, two R wherein
aGroup forms symmetrical chain, perhaps Y together
1=SiR
cR
dAnd Y
2=SiR
cR
d, two R wherein
cGroup forms symmetrical chain together.
For platinum complex of the present invention (a), mention the first special preferred classes of the metal complexes of following formula (I.1) suitably:
Wherein:
T
1And T
2Identical and as above the definition;
T
3And T
4As above definition;
R
cAnd R
dAs above definition.
The metal complexes that comprises following formula (I.2) according to the second special preferred classes of the catalyzer-C-of composition of the present invention:
Wherein:
T
1And T
2Identical and as above the definition;
T
3And T
4As above definition;
R
cAnd R
dAs above definition.
The metal complexes that comprises following formula (I.3) according to the 3rd special preferred classes of title complex of the present invention (a):
Wherein:
T
1And T
2Identical and as above the definition;
T
3And T
4As above definition;
R
cAnd R
dAs above definition.
The preparation of the metal complexes of the formula of touching upon below (I).These title complexs can be obtained by title complex (I), wherein L
γHave formula (II) and L
αAnd L
βForm the part of formula (IV) together, the latter is substituted by formula (III.1) or compound original position (III.2).
L wherein
γHave formula (II) and L
αAnd L
βThese title complexs (I) that form formula (IV) part are together for example prepared by ligand exchange by the known title complex of prior art traditionally, that is to say that the suitable Cabbeen by adding type (II) in the platinum title complex of the solution form that is known as the precursor title complex prepares.
Suitable precursor title complex for example is the Karstedt title complex of following formula:
Pt
2[ViMe
2Si-O-SiMe
2Vi]
3
Wherein Vi represents vinyl.
These parts are commercially available, perhaps prepared by the commercial compound by those skilled in the art easily.For further details, can be with reference to the information that provides among the WO-A-01/42258, the particularly document the 15th to 18 page.
The Cabbeen of formula (II) can pass through imidazoles
Salt, tetrazolium
Salt, triazole
Salt or pyrazoles
The deprotonation of salt prepares, as the situation under the alkali effect.
These reactions can as followsly be carried out:
In these reaction formula, T
1, T
2, T
3, T
4, A and B have as above at the given definition of formula (I), and X
-Represent negatively charged ion.
According to the present invention, negatively charged ion X
-Character be not key factor.Negatively charged ion X
-It is the negatively charged ion that is derived from organic or inorganic Bronsted acid (protonic acid).Usually, negatively charged ion X
-Be derived from pKa less than 6 acid.Preferably, X
-Be derived from pKa less than 4, better less than 2 acid.Related herein pKa value is the pKa value of the acid that records in water.
The example of acid is: carboxylic acid, for example acetate, phenylformic acid or stearic acid; Sulfonic acid, for example Phenylsulfonic acid; And phosphonic acids, for example phenyl-phosphonic acid.
According to the present invention, more particularly preferably be and be derived from sour HF, HCl, HBr, HI, H
2SO
4, HBF
4And H
3PO
4Negatively charged ion X
-
The alkali of deprotonation that can be used for the salt of formula (VIII.1) is the highly basic that is selected from alkalimetal hydride, alkali metal hydroxide, alkali metal carboxylate, alkali metal alcoholates and alkali metal amide.
Therefore the example of suitable alkali is sodium hydride, sodium methylate, potassium tert.-butoxide, LDA and their mixture.
Hydrogenation reaction is preferably carried out in the solvent of the raw material salt that can be partly dissolved formula (VIII.1) at least and other reactant.
The character of solvent also depends on the intensity of alkali.This is because under the situation of highly basic and particularly reactive raw material salt, may need to operate at low temperatures.
Usually, temperature of reaction is 40 ℃ to-78 ℃, and preferred 30 to-50 ℃ is 25 to-40 ℃ better, for example 20 to-30 ℃.
The available solvent is cyclic ethers or acyclic ether in the preparation method of Cabbeen, for example diethyl ether, diisopropyl ether, tetrahydrofuran (THF), two
Alkane, glycol dimethyl ether or diglyme.
In WO-A-01/42258, the method for the Cabbeen of preparation formula (II) has been described in the 20th and 21 page particularly.
According to particularly preferred embodiment of the present invention, metal complexes of the present invention has following formula:
L wherein
γAs above definition.
The simple method for preparing this title complex is to make Cabbeen L
γWith average formula be Pt
2[ViMe
2Si-O-SiMe
2Vi]
3The Karstedt catalyst reaction, wherein Vi represents vinyl.
This reaction can be carried out or carry out in solvent by body.
The example of appropriate solvent is cyclic ethers or acyclic ether, acid amides and aromatic hydrocarbons.
Temperature of reaction is generally 10 to 50 ℃, and preferred 15 to 35 ℃, very preferably 20 to 25 ℃.Operation is desirable in the presence of the Cabbeen excessive slightly with respect to platinum.
About implementing the further details of this reaction, can be with reference to the information that provides among the WO-A-02/098971, the particularly document the 40th to 43 page.
Following completion is at combination b) situation under the definition of other platinum complex of using.
The preferred classes of described other platinum complex comprises following material:
-chloroplatinic acid H
2PtCl
6And derivative;
-Shi (PtCl
2Alkene)
2Title complex, the alkene of this title complex is meant ethene, propylene, butylene, tetrahydrobenzene or vinylbenzene especially; With
The title complex of-platinum and vinylated organopolysiloxane, for example Karstedt catalyzer particularly.
The definition of silicon composition
The curable polyorganosiloxane composition C involved in the present invention that provides in one or several packings (single component or polycomponent) comprises that enhancing or half that the main component that formed by one or more organopolysiloxane compositions, suitable catalyzer and optional one or more are selected from the rheological that is used for regulating curable compositions especially strengthens or the compound of the supplementary additive that increment filler and this technical field are commonly used.
Organopolysiloxane as the main component of composition C involved in the present invention can be straight chain, branching or crosslinked, and the reactive group that can comprise alkyl and/or be formed by thiazolinyl and hydrogen atom.Should be noted that, in the literature, particularly at the works " Chemistry and Technology of Silicones " of Walter Noll, Academic Press, 1968, second edition has fully been described constituent polyorganosiloxane composition in the 386th to 409 page.
More specifically, form by the siloxy units of logical formula V and/or the siloxy units of formula (VI) as the organopolysiloxane of the main component of composition C involved in the present invention:
In these formulas, each symbol has following meanings:
-symbol R is identical or different, represents the group of non-hydrolysable hydrocarbon character separately, and this group can be:
★ has 1 to 5 carbon atom and comprises the alkyl or the haloalkyl of 1 to 6 chlorine and/or fluorine atom,
★ has 3 to 8 carbon atoms and comprises the cycloalkyl and the halogenated cycloalkyl of 1 to 4 chlorine and/or fluorine atom,
★ has 6 to 8 carbon atoms and comprises aryl, alkylaryl and the halogenated aryl of 1 to 4 chlorine and/or fluorine atom,
★ has the cyano group alkyl of 3 to 4 carbon atoms;
-symbols Z is represented hydrogen atom or C separately
2-C
6Thiazolinyl;
The integer that-n=equals 0,1,2 or 3;
The integer that-x=equals 0,1,2 or 3;
The integer that-y=equals 0,1 or 2;
The summation of-x+y is 1 to 3.
As an example, among the organic group R on being bonded directly to Siliciumatom, can mention: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, n-pentyl, the tertiary butyl, chloromethyl, dichloromethyl, α-chloroethyl, α, β-Dichloroethyl, methyl fluoride, difluoromethyl, α, β-two fluoro ethyl, 3,3, the 3-trifluoro propyl, the trifluoro cyclopropyl, 4,4,4-trifluoro butyl, 3,3,4,4,5,5-hexafluoro amyl group, β-cyanoethyl, γ-cyanogen propyl group, phenyl, rubigan, between chloro-phenyl-, 3, the 5-dichlorophenyl, trichlorophenyl, the tetrachloro phenyl, adjacent-, right-or-tolyl, α, α, α-fluoroform phenyl or xylyl, for example 2,3-3,5-dimethylphenyl or 3,4-3,5-dimethylphenyl.
Preferably, the organic group R that is bonded on the Siliciumatom is a methyl or phenyl, and these groups can be chosen wantonly by halogenation, or the cyano group alkyl.
Symbols Z is hydrogen atom or thiazolinyl, and it is preferably vinyl.
As known, according to selecting the type of organopolysiloxane and siloxy units thus (V) and the ratio of siloxy units (VI) and their distribution for curable compositions being changed into the crosslinking Treatment that elastomerics carries out said composition.
Two-pack or single component constituent polyorganosiloxane composition C have for example been described in patent US-A-3 220 972,3 284 406,3 436 366,3 697 473 and 4 340 709, said composition C is by polyaddition, the at room temperature crosslinked or heat cross-linking of reaction in the presence of metal catalyst (normally platinum based catalyst) by hydrogenation silyl and thiazolinyl silyl basically.Normally, the organopolysiloxane that comprises in these compositions is by on the one hand based on representing C by the Z residue
2-C
6Thiazolinyl and x equal at least 1 o'clock unit (VI) optional combine formed straight chain, branching or cross linking polysiloxane with unit (V) and choose wantonly based on the unit (VI) of representing hydrogen atom and x to equal at least by the Z residue at 1 o'clock on the other hand combine formed straight chain, branching or crosslinked hydrogenated polysiloxane with unit (V) and form in twos.
Be known as under the situation of passing through the crosslinked composition C of polyaddition of RTV, the organopolysiloxane composition that has the thiazolinyl silyl advantageously has at 25 ℃ and equals 10000mPas at most, preferred 200 to 5000mPas viscosity.
Be known as under the situation of passing through the crosslinked composition C of polyaddition of LSR, the organopolysiloxane composition that has a thiazolinyl silyl have 25 ℃ greater than 1000mPas, the viscosity of preferred 5000mPas to 200000mPas.
Under the situation of passing through the crosslinked composition C of polyaddition that is being known as poly-addition HCE, the organopolysiloxane composition that has a thiazolinyl silyl have 25 ℃ greater than 300000mPas, preferred 100 ten thousand mPas to 3,10,000,000 mPas even higher viscosity.
Under the situation of the constituent polyorganosiloxane composition C that is known as RTV, LSR or poly-addition HCE, the organopolysiloxane composition that has the hydrogenation silyl has usually at 25 ℃ and equals 10000mPas at most, preferred 5 to 1000mPas viscosity.
Described composition can also be at high temperature at the composition C of organo-peroxide effect curable.Be known as organopolysiloxane contained in this composition of HCE or glue (gomme) is then formed by siloxy units (V) basically, C is randomly represented with the Z residue in this unit
2-C
6Unit (VI) combination that thiazolinyl and x equal 1.This class HCE has for example been described in patent US-A-3142 655,3 821 140,3 836 489 and 3 839 266.
The organopolysiloxane composition of these HCE compositions advantageously has at 25 ℃ and equals 300000mPas at least, preferred 100 ten thousand to 3,000 ten thousand mPas even higher viscosity.
Curable compositions C involved in the present invention can also comprise catalyzer and the supplementary additive of choosing wantonly, be used to regulate the enhancing or half enhancing or the increment filler of rheological except the organopolysiloxane composition, be preferably selected from siliceous filler.
Reinforcing filler is selected from pyrogenic silica and precipitated silica usually.They have the 50m at least that records according to the BET method
2/ g is preferably greater than 100m
2The specific surface area of/g, and less than the average particle size particle size of 0.1 micron (μ m).
These silicon-dioxide are former state or be impregnated in after handling with the silicoorganic compound that are usually used in this purposes preferably.These compounds comprise methyl polysiloxane, for example hexamethyldisiloxane or octamethylcyclotetrasiloxane; Methyl polysilicon azane, for example hexamethyldisilazane or pregnancy basic ring three silazane; Chlorosilane, for example dimethyldichlorosilane(DMCS), trimethylchlorosilane, methyl ethylene dichlorosilane or dimethyl vinyl chlorosilane; Or organoalkoxysilane, for example dimethyldimethoxysil,ne, dimethyl vinyl Ethoxysilane or trimethylammonium methoxy silane.Herein in the reason process, it is about at most 20% that silicon-dioxide can improve its starting weight, preferably approximately 10%.
Can be used for regulating that half of rheological strengthens or the increment filler has less than 100m
2The BET specific surface area of/g and greater than 0.1 micron average particle size particle size, and be preferably selected from and grind quartz, calcined clay, diatomite and zirconium white.
When needs,, can use 0.5 to 200 weight %, the filler of preferred 1 to 150 weight % with respect to the weight of the organopolysiloxane composition of composition C.
Among the present invention preferred constituent polyorganosiloxane composition C be known as RTV pass through polyaddition crosslinked at ambient temperature or the single component of heat cross-linking or those compositions of two-pack, it comprises:
(a) at least a polydiorganosiloxane of 100 weight parts, being selected from per molecule has at least 2 and is bonded to type homopolymer and the multipolymer that is arranged in the vinyl on chain and/or the terminated Different Silicon atom, its other organic group that is bonded on the Siliciumatom is selected from methyl, ethyl and phenyl, at least 60 moles of % of these other groups (preferably all these other groups) are methyl, and it has the average viscosity at 25 ℃ following 200 to 5000mPas;
(b) at least a poly-Organhydridosiloxaneresins, be selected from per molecule and on average have at least 2 line style or ring-type homopolymer and multipolymers that are bonded to the hydrogen atom on the Different Silicon atom, its organic group that is bonded on the Siliciumatom is selected from methyl, ethyl and phenyl, at least 60 moles of % of these groups (preferably all these groups) are methyl, and it has the viscosity at 25 ℃ following 5 to 1000mPas, and the consumption of reactant (b) makes that the molar ratio of the hydride functionalities of (b) and vinyl (a) is 1.0 to 10;
(c) platinum catalyst of catalytically effective amount;
(d) per 100 weight part organopolysiloxane (a)+(b) are combined as 0 to 120 weight part, the siliceous filler of preferred 0 to 100 weight part.
In another embodiment, the reactant of maximum 100 weight % (a) is comprised 0.1 to 20 weight % vinyl in its structure organopolysiloxane resin replaces, and described structure has at least two different unit M (three organic siloxyies), D (two organic siloxyies), T (single organic siloxy-) and Q (SiO of being selected from
4/2) the unit, at least one unit in these unit is T or Q unit, vinyl can be carried by M, D and/or T unit.
Reactant (a) can advantageously be the line style polydiorganosiloxane, and the unit (V) of its chain during basically by n=2 forms, and this chain is at unit (VI) end-blocking of each end during by Z=vinyl and x=1 and y=2.
Reactant (b) can advantageously be: comprise at least 3 poly-Organhydridosiloxaneresins of line style that are bonded to the hydrogen atom on the silicon in its structure, its chain basically by optional during with n=2 unit (V) bonded Z=H and the unit (VI) during x=y=1 form, this chain is at the unit (VI) of each end during by Z=H and x=1 and y=2 or unit (V) end-blocking during by n=3; Or the mixture of described poly-Organhydridosiloxaneresins and the poly-Organhydridosiloxaneresins of another line style, the unit (V) of the chain of the poly-Organhydridosiloxaneresins of this another line style during basically by n=2 forms, and this chain is at unit (VI) end-blocking of each end during by Z=H and x=1 and y=2.
The weight content of the catalyzer (C) that calculates by the parts by weight of platinum is generally 1 to 250ppm, and preferred 2 to 100ppm, based on the weight meter of organo-siloxane (a)+(b) combination.
Other preferred constituent polyorganosiloxane composition C is those compositions that are known as the single component of passing through the polyaddition heat cross-linking or the two-pack of LSR composition.These compositions corresponding to as above at the given definition of the preferred composition that is known as RTV, be the viscosity of vinylated polydiorganosiloxane reactant (a) at this for greater than 1000mPas and be preferably more than the value of 5000mPas to 200000mPas.
Other preferred constituent polyorganosiloxane composition C is known as the single component of passing through the polyaddition heat cross-linking of poly-addition HCE composition or those compositions of two-pack, and it comprises:
At least a polydiorganosiloxane glue of (a ') 100 weight parts, it is that per molecule has at least 2 and is bonded to type homopolymer or the multipolymer that is arranged in the vinyl on chain and/or the terminated Different Silicon atom, its other organic group that is bonded on the Siliciumatom is selected from methyl, ethyl, phenyl, at least 60 moles of % of these other groups (preferably all these other groups) are methyl, and described glue has under 25 ℃ the viscosity greater than 300000mPas and preferred at least 1 hundred ten thousand mPas;
(b ') at least a poly-Organhydridosiloxaneresins, be selected from per molecule and have at least 3 line style, ring-type or netted homopolymer or multipolymers that are bonded to the hydrogen atom on the Different Silicon atom, its organic group that is bonded on the Siliciumatom is selected from methyl, ethyl, phenyl, at least 60 moles of % of these groups (preferably all these groups) are methyl, and it has the viscosity at 25 ℃ following 5 to 1000mPas, the molar ratio of the vinyl of hydride functionalities with (a ') that the consumption of reactant (b ') makes (b ') is 0.4 to 10, preferred 1.1 to 7;
The platinum catalyst of (c ') catalytically effective amount;
(d ') per 100 weight part organopolysiloxane (a ')+(b ') are combined as 0.5 to 120 weight part, the siliceous filler of preferred 1 to 100 weight part.
This glue (a ') forms along the unit (V) of its chain during by optional unit (VI) bonded n=2 during with Z=vinyl and x=y=1, and at each end of its chain unit (VI) during by Z=vinyl and x=1 and y=2 or unit (V) end-blocking during by n=3.
Advantageously, as composition (b '), use at least a line style to gather Organhydridosiloxaneresins, its chain basically by optional during with n=2 unit (V) bonded Z=H and the unit (VI) during x=y=1 form, this chain is at the unit (VI) of each end during by Z=H and x=1 and y=2 or unit (V) end-blocking during by n=3.
Represent with respect to the parts by weight of the weight of described glue (a ') and hydrogenation silyl compound (b ') that with platinum the weight content of catalyzer (C ') is 1 to 250ppm, preferred 3 to 100ppm.
Other preferred constituent polyorganosiloxane composition C is those compositions that are known as the single component of HCE in addition, and it comprises:
(at least a polydiorganosiloxane glue of a ") 100 weight parts; it is that per molecule has at least 2 and is bonded to type homopolymer or the multipolymer that is arranged in the vinyl on chain and/or the terminated Different Silicon atom; its other organic group that is bonded on the Siliciumatom is selected from methyl, ethyl, phenyl; at least 60 moles of % of these other groups (preferably all these other groups) are methyl, and described glue has under 25 ℃ the viscosity of 300000mPas at least and preferred at least 1 hundred ten thousand mPas;
(the organo-peroxide of b ") 0.1 to 7 weight part;
(c ") per 100 weight part glue (a ") be 0.5 to 120 weight part, the siliceous filler of preferred 1 to 100 weight part.
Glue (a ") can advantageously be: the line style polydiorganosiloxane; the unit (V) of its chain during basically by optional unit (VI) bonded n=2 during with Z=vinyl and x=y=1 forms, and at each end of its chain unit (VI) end-blocking during by Z=vinyl and x=1 and y=2; Or the mixture of described polydiorganosiloxane and another line style polydiorganosiloxane, the chain of this another line style polydiorganosiloxane during basically by n=2 unit (V) and the unit (VI) when Z=vinyl and x=y=1 form, this chain is at unit (V) end-blocking of each end during by n=3.
Organo-peroxide (b ") is 0.1 to 7 part with per 100 parts of glue (a "), and preferred 0.5 to 3 part ratio is used.They are that the professional is known and especially comprise benzoyl peroxide, peroxidation 2,4-dichloro-benzoyl, dicumyl peroxide, 2, two (t-butyl peroxy)-2 of 5-, 5-dimethylhexane, t-butylperoxyl benzoate, BPIC (t butyl peroxy isopropyl carbonate), di-t-butyl peroxide, 1, two (t-butyl peroxy)-3 of 1-, 3, the 5-trimethyl-cyclohexane.
With with respect to curable compositions C[(a+b) or (a '+b ') or (a ")] the elements platinum parts by weight of gross weight of organopolysiloxane composition represent; the amount that is used as the specific platinic compound [additive (a)+optional (b)] of stablizer is generally 1 to 250ppm; preferred 2 to 100ppm, and more preferably 3 to 70ppm.
Under the situation of the composition of RTV, LSR or poly-addition HCE type, used platinum stablizer can advantageously serve as the catalyzer of the crosslinked polyaddition of control curable compositions C simultaneously under the situation of above-mentioned consumption.
Except mentioned component [(a) and (b), (c) and (d)], [(a '), (b '), (c ') and (d ')] or [(a "), (b ") and (c ")]; silicon composition C also randomly comprises supplementary additive (e) in addition, for example particularly: the product (e1) of at least a what is called " anti-structurizing (anti-structure) "; And/or at least a polyorganosiloxane resin (e2); And/or at least a reagent (e3) based on metal oxide or oxyhydroxide or salt; And/or at least aly be used to produce articles colored pigment (e4); And/or at least a boryl compound (e5); And/or the filler (e6) of at least a fusion (fondant) type and/or stratiform type, they can with or can not be used in combination under the situation of catching fire, to cause forming the insulating ashy substance with one or more suitable mineral materials; And/or at least a adhesion promotor (e7); Be known as under the situation of passing through the crosslinked silicon composition C of polyaddition of RTV, LSR or poly-addition HCE, and/or at least a crosslinked retarding agent (e8).
More specifically, during in using them one or more, supplementary additive (e) be expressed as [for per 100 weight part organo-siloxanes polymers (a+b) or (a '+b ') or (a ")]:
" anti-structurizing " product (e1) of-0.1 to 15 weight part, its based on for example 25 ℃ of viscosity be 10 to 3000mPas and at each end of the chain by hydroxyl or the end capped polydimethyl siloxane oil of methoxyl group, and/or based on 25 ℃ of viscosity be 10 to 1000mPas and at each end of the chain by end capped poly-(methyl ethylene) silicone oil of hydroxyl or methoxyl group, and/or based on 25 ℃ of viscosity be 10 to 1000mPas and at each end of the chain by hydroxyl or end capped poly-(aminomethyl phenyl) silicone oil of methoxyl group; And/or
-0.1 to 5 part of polyorganosiloxane resin (e2), it is expressed as: comprise R basically
3SiO
0.5And SiO
2Unitary " MQ " resin, wherein R
Representative has the optional halogenated univalence hydrocarbyl that is less than 7 carbon atoms, R
3SiO
0.5With SiO
2Weight ratio be 0.5/1 to 1/2/1; Basically comprise HR
2SiO
0.5And SiO
2Unitary M ' Q resin, wherein R
Has above-mentioned implication, HR
2SiO
0.5With SiO
2Weight ratio be 0.5/1 to 10/1; And/or
-0.01 to 10 part of reagent (e3), for example particularly: metal salts of organic acids, for example iron or cerium salt, for example iron octoate or cerium octoate (ratio more specifically is 0.01 to 1 part); Cerium oxide, cerous hydroxide, titanium oxide or ferric oxide (ratio more specifically is 0.1 to 10 part); Oxide compound CaO, oxide M gO (ratio more specifically is 0.01 to 0.4 part); Zirconium white; Hydration or anhydrous alumina; And/or
-0.01 to 5 part of tinting pigment (e4); And/or
-0.01 to 3 part of boryl compound (e5), for example boric acid and derivative thereof, alkyl ester type for example, this alkyl has 1 to 3 carbon atom; And/or
-0.2 to 30 part of filler (e6), this filler are the filler such as the ZnO of melt type, and/or the filler of stratiform type such as mica, its randomly with metal oxide TiO
2And/or wollastonite combination; And/or
-0.01 to 2 part of adhesion promotor (e7), it for example is selected from and has (1) and be bonded to the silicoorganic compound that hydrolysable group on the Siliciumatom and (2) are selected from the organic group that isocyanato, epoxy group(ing), thiazolinyl, isocyanuric acid ester group and (methyl) acrylate-based group replace; And/or
-0.005 to 5 part, preferred 0.01 to 3 part of crosslinked retarding agent (e8), it for example is selected from: organic amine, silazane, organic oxime, dicarboxylic diester, acetylene series ketone, especially, preferred inhibitors is unit (V) the bonded ring-type polydiorganosiloxane during with n=2 that acetylene alcohol (for example referring to FR-A-1 528 464,2 372 874 and 2 704 553) and the unit (VI) during basically by Z=vinyl and x=y=1 form and optional.
Therefore, the constituent polyorganosiloxane composition C that comprises stabilising additive in addition can be a single-component composition, that is to say in unitary package and loads; If said composition must store before using, what then may wish is that interpolation is to the inhibitor (above stating) of the significant quantity of the katalysis of platinum under the situation of RTV, LSR and poly-addition HCE composition, and this inhibition is owing to the heating in the composition cross-linking process disappears.These composition C that comprise stabilising additive in addition can be two-component compositions also, that is to say in two independent packings and load, and wherein have only one to comprise crosslinking catalyst; In order to obtain elastomerics, with the contents mixed of two packings, and it is crosslinked to rely on catalyzer to take place.This single component and two-component composition are known in those skilled in the art.
Be to produce elastomerics, comprise in addition curable compositions C crosslinked of stabilising additive can be according to the type (RTV, LSR, poly-addition HCE or HCE) of composition therefor according to known mode itself in envrionment temperature (23 ℃) or under 40 ℃ to 250 ℃, carry out.
Embodiment
The following examples provide in the mode of explanation, and they should not be considered to limit the scope of the invention.
Embodiment 1 to 5:
1.
The preparation of the Cabbeen of following formula:
(referring to Chem.Eur.J., 1996,2,1627).
Reaction hereto, all used glasswares all 150 ℃ of dried overnight in stove, cool off under argon gas then.
Before just will using, on sodium/benzophenone, distill THF.
In 100 milliliters of three-necked flasks, pack into 2.70 the gram (10 mmole) chlorinations 1,3-dicyclohexyl imidazoles
, purge with argon gas stream then, be suspended in then among 20 milliliters of THF.About 50 milliliters of ammonia are condensed in the three-necked flask at-78 ℃, thereby this salt is partly dissolved.Remove acetone/the dry ice bath, and use the charge solids device slowly to add 270 milligrams of 95%NaH (10.7 mmoles, 1.07 equivalents).Each NaH that adds obviously discharges gas (H afterwards
2), and the salt that suspends dissolves gradually.Reaction mixture was stirred under the situation of solvent refluxing 1 hour 30 minutes.Vaporized ammonia, and the solid (NaCl) of acquisition pale yellow solution and suspension subsequently.This solution (its Cabbeen concentration in THF is 0.5M) is used for the preparation of title complex immediately.
2.
The preparation of the platinum-arbine complex of following formula:
Prepare the Karstedt solution that comprises 10 weight % platinum (i.e. 1.52 mmole platinum) according to the schedule of operation described in the US 3 775 452.
Use dropping funnel, in 3 these solution of gram, dropwise add the 0.5M solution of Cabbeen in tetrahydrofuran (THF) of 3.2 milliliters of following formulas:
Keep stirring and in 10 milliliters of tetrahydrofuran (THF)s, diluting.This is added on after 10 minutes and finishes.Reaction mixture stirred 50 minutes subsequently at ambient temperature.If necessary, the insoluble light materials of filtering, and reaction mixture is concentrated under vacuum.
After concentrating, obtain light yellow adhesive residue.In a few hours, from residual divinyl tetramethyl disiloxane, be settled out a large amount of white solids.With its filtering and with several milliliters of hexamethyldisiloxane washings, wash with pentane then.Obtain 570 milligrams of (60% yield) analytically pure white powders thus.
The part of this powder of recrystallize in methylene dichloride/dehydrated alcohol mixture.Analyze the gained crystal by X-ray diffraction.The structure of this analysis confirmation gained title complex.
3.
The preparation of silicon composition:
Following material is mixed in the arm-type batch mixer of Z-under envrionment temperature (23 ℃):
By the unit terminated polydimethylsiloxane of dimethylvinylsiloxy, it comprises the dimethylvinylsiloxy end group of 450ppm to-92 weight parts at its each end;
-8 weight parts at each end of two end by unit terminated poly-(dimethyl) (methyl ethylene) siloxanes of trimethylsiloxy, it comprises 76 000ppm in chain methyl ethylene siloxy-has the viscosity at 25 ℃ of following 400000mPas;
By the unit terminated polydimethyl siloxane oil of present as dimethylhydroxysilox(, it comprises the OH of 8.5 weight % to-3.3 weight parts at two end, is 50mPas 25 ℃ viscosity;
-33 weight parts have a 150m
2The pyrogenic silica of/g specific surface area; With
The powdery calcium oxide of-0.3 weight part.
After homogenizing, the gained mixture is divided into several parts.Process each uniform parts on the double shaft mixer of operation at ambient temperature subsequently, introduce following material thus:
-platinic compound, its character and ratio are presented in the following table 1 (shown in ratio represent with the ppm of platinum with respect to total composition weight);
-for the per 100 parts mixtures of wanting crosslinked uniform parts, 50 weight % peroxidation 2,4 dichloro benzene formyls of 1.25 weight parts.
Table 1
(*): the title complex of making according to the schedule of operation described in the above-mentioned the 1st and 2 parts
4. the sign of said composition:
By hot pressing in suitable mold, with each partial vulcanization, this makes it possible to produce the thick sample strip that becomes 2 millimeters; This sulfuration was carried out under 115 ℃ 10 minutes.
By coming evaluation temperature stability by the thermogravimetric analysis gained residuals content that uses Mettler TGA thermobalance; According to temperature is risen to 700 ℃ schedule of operation with 80 ℃/minute speed, carry out this operation at 20 milligrams of fragments that extract from sample strip.
Gained the results are shown in the following table 2:
Table 2: the weight loss of % meter by weight
Result in the last table 2 clearly shows the performance similarity that writes down when using Platinic chloride and Karstedt platinum, and when using platinum-arbine complex, from minimum ratio, it is much lower to degrade.
Embodiment 6 and 7:
1.
The preparation of silicon composition
In the turbine mixer of laboratory, introduce following material:
The suspension of-74.8 weight parts, this suspension comprises:
● the pyrogenic silica of 14.96 weight parts, its BET specific surface area is 200m
2/ g carries out surface treatment (according to document WO-A-98/58997, the indication that provides in the 6th to 19 page) with hexamethyldisilazane;
● 59.84 weight parts at each end of chain by the unit terminated polydimethyl siloxane oil of dimethylvinylsiloxy, it is 25 ℃ of viscosity with 1600mPas;
The premixture of-17.3 weight parts, it comprises: 25 ℃ have 2000mPas viscosity in each end of chain polydimethyl siloxane oil unit terminated by dimethylvinylsiloxy, the grinding quartz of 40 weight %; The titanium oxide of 8 weight %; 0.3 the methacryloxypropyl trimethoxy silane of weight %;
3,7 of-0.075 weight part, 11-trimethylammonium-1-dodecyne-3-alcohol; With
Each end at chain of-6.85 weight parts is hydrogenated unit terminated poly-(dimethyl) (methylol) silicone oil of dimethylsilane oxygen base, it has the viscosity of 25mPas under 25 ℃, and totally comprise 7.9 weight %Si-H functional groups, comprise the Si-H functional group of 6 weight % from hydrogenation methyl-silicane oxygen base internal element.
After homogenizing, the gained mixture is divided into several parts.At ambient temperature, introduce platinic compound in each uniform parts, its character and ratio are as (shown in ratio represent with the ppm of platinum with respect to total composition weight) as shown in the following table 3;
Table 3
(*): the title complex of making according to the schedule of operation described in the 1st and 2 parts of the foregoing description 1 to 5
2.
The sign of said composition:
In the following manner with each partial vulcanization: after the degassing, this part is cast in the suitable mould that itself places draft furnace, at first 80 ℃ following 1 hour, then 120 ℃ of following another hours.
By coming evaluation temperature stability by the thermogravimetric analysis gained residuals content that uses Mettler TGA thermobalance; According to temperature is risen to 700 ℃ schedule of operation with 20 ℃/minute speed, carry out this operation at 20 milligrams of fragments that extract from sample strip.
Gained the results are shown in the following table 4:
Table 4: the weight loss of % meter by weight
The another way of evaluate temperature stability is the monitoring elastomerics in the variation of the Xiao A hardness of 250 ℃ of annealing after 36 hours (according to the feature of the conditioned measurement of standard DIN 53505).Gained the results are shown in the table 5:
Table 5
Benefit when listed result demonstrates separately or be used in combination with Karstedt platinum platinum-arbine complex in the table 4 and 5.
Claims (16)
- Platinum in being intended to obtain the constituent polyorganosiloxane composition C of silicone elastomer as improving the anti-purposes that is higher than the stabilising additive of degradation property under 500 ℃ the ultrahigh-temperature effect of silicone elastomer, said composition at high temperature crosslinked or crosslinked at ambient temperature or heat cross-linking of polyaddition by in the presence of metal catalyst under the organo-peroxide effect wherein, described purposes is characterised in that platinum is at least a form that is selected from following compound:A): at least a platinum complex that is selected from the product of formula (I):Wherein:Wherein:A and B represent C or N independently, it should be understood that when A represents N T 4Without any implication, when B represents N, T 3Without any implication;T 3And T 4Represent hydrogen atom independently; Alkyl; Optional by the cycloalkyl of alkyl or alkoxyl group replacement; Optional by the aryl of alkyl or alkoxyl group replacement; Thiazolinyl; Alkynyl; Or arylalkyl, wherein aryl moiety is optional is replaced by alkyl or alkoxyl group; PerhapsT 1And T 2Represent alkyl independently; Perfluorinated alkyl; Optional by the cycloalkyl of alkyl or alkoxyl group replacement; Optional by the aryl of alkyl or alkoxyl group replacement; Thiazolinyl; Alkynyl; Or arylalkyl, wherein aryl moiety is optional is replaced by alkyl or alkoxyl group; PerhapsV 1-V 2 (V)Wherein:V1Be bivalent hydrocarbon radical,V 2Be to be selected from following substituent monoradical:W 1-ω-W 2 (W)Wherein:W 1Be bivalent hydrocarbon radical,The ω representative:-R 1C=CR 1-R wherein 1Corresponding to H or alkyl, perhaps-C≡C-W 2Be to be selected from following substituent monoradical:R 2=alkyl or H;Perhaps, substituting group T 1, T 2, T 3And T 4Can form saturated in twos or aliphatic unsaturated hydrocarbon when being arranged in when two adjacent ring members of formula (II) go up;Wherein, in these formulas (III.1) with (III.2):Z 1, Z 2, Z 3, Z 4, Z 5And Z 6Representative independently of one another:A. hydrogen,B. halogen,C. cyano group,D. saturated or unsaturated electrophilic alkyl,E. two adjacent Z 1To Z 6Can form Cabbeen L together with formula (II) γThe different also optional heteroatomic electrophilic rings that comprise;Perhaps, substituting group Z 1And Z 2Form the unit price thiazolinyl together in (III.1), this unit price thiazolinyl comprises at least one electrophilic residue,Perhaps, Z 3To Z 6Form the unit price thiazolinyl in (III.2) in twos, this unit price thiazolinyl comprises at least one electrophilic residue;Perhaps form the ligand L of formula (IV) together δ:Wherein:Y 1And Y 2Represent CR independently of one another aR bOr SiR cR dX represents O, NR eOr CR fR gR 10, R 11, R 13And R 14Identical or different, be selected from hydrogen atom, alkyl or the optional aryl that is replaced by alkyl;R 9, R 12, R a, R bAnd R eBe independently selected from hydrogen atom; Alkyl; Acyl group; The optional aryl that is replaced by alkyl; The optional cycloalkyl that is replaced by alkyl; And arylalkyl, wherein aryl moiety is optional is replaced by alkyl;R cAnd R dBe independently selected from alkyl; The optional aryl that is replaced by alkyl; The optional cycloalkyl that is replaced by alkyl; And arylalkyl, wherein aryl moiety is optional is replaced by alkyl; PerhapsWork as Y 1And Y 2Represent SiR independently cR dThe time, be bonded to two R on two Different Silicon atoms cGroup forms the chain of following formula together:Wherein n is 1 to 5 integer; X as above defines; R and R ' are identical or different, have as above at R cOr R dIn the implication that provides any one;PerhapsWork as Y 1And Y 2Represent SiR independently cR dThe time, be bonded to two R on the Different Silicon atom cGroup forms saturated hydrocarbon chain together, these two R cGroup forms 6-to 10-unit ring with described Siliciumatom and X; PerhapsWork as Y 1And Y 2Represent CR independently aR bThe time, be bonded to two R on the different carbon atoms aGroup forms saturated hydrocarbon chain together, these two R aGroup forms 6-to 10-unit ring with carbon atom that carries them and x; AndR fAnd R gRepresent hydrogen atom independently of one another; Alkyl; Acyl group; The optional aryl that is replaced by alkyl; The optional cycloalkyl that is replaced by alkyl; Arylalkyl, wherein aryl moiety is optional is replaced by alkyl; Halogen atom; Thiazolinyl; Alkynyl; Or SiG 1G 2G 3Group, wherein G 1, G 2And G 3Be alkyl independently of one another; Alkoxyl group; Optional by the aryl of alkyl or alkoxyl group replacement; Or arylalkyl, wherein aryl moiety is optional is replaced by alkyl or alkoxyl group;B): (a) with the combination of at least a other platinum complex, this at least a other platinum complex is selected from: the title complex of 0 oxidation state platinum, the title complex of+2 oxidation state platinum or+title complex of 4 oxidation state platinum.
- 2. the purposes of claim 1 is characterized in that, in the carbenes of formula (II):And/or T 1And T 2Identical or different, representative (C 1-C 8) alkyl or (C 3-C 8) cycloalkyl or allyl group-CH 2-CH=CH 2Or methylallyl-CH 2-C (CH 3)=CH 2Or propargyl-(CH 2) 2-C ≡ CH,PerhapsPerhaps-(CH 2) γ=1 is to 4-aminePerhaps-(CH 2) γ=1 is to 4-alkoxyl group; And/or A and B represent carbon atom.
- 3. claim 1 or 2 purposes is characterized in that in formula (III.1) with (III.2), the electrophilic residue is selected from:Wherein: R 17, R 18, R 19Or R 20Be replacement or unsubstituted alkyl, thiazolinyl, alkynyl or trialkylsilkl, n ' is 1 to 50.
- 4. each purposes of claim 1 to 2 is characterized in that L αAnd L βForm the ligand L of formula (IV) together δ, Y wherein 1And Y 2All represent CR aR bAll represent SiR cR d, make described title complex be formula (IV.1) or be the title complex of formula (IV.2):Wherein:Two R aGroup, two R bGroup, two R cGroup and two R dGroup is mutually the same, and R 9=R 12R 10=R 14And R 11=R 13
- 6. each purposes of claim 1 to 2 is characterized in that b) be a) with the combination of other platinum complex, this other platinum complex is selected from:-chloroplatinic acid H 2PtCl 6-Shi (PtCl 2Alkene) 2Title complex, the alkene of this title complex is meant ethene, propylene, butylene, tetrahydrobenzene or vinylbenzene; WithThe title complex of-platinum and vinylated organopolysiloxane.
- 7. each purposes of claim 1 to 2, it is characterized in that, represent that with elements platinum parts by weight the amount of specific platinic compound [stabilising additive (a)+optional (b)] is 1 to 250ppm with respect to the organopolysiloxane composition gross weight of curable compositions C.
- 8. each purposes of claim 1 to 2 is characterized in that the curable polyorganosiloxane composition C that provides comprises that the main component that formed by one or more organopolysiloxane compositions, suitable catalyzer and optional one or more are selected from the rheological that is used to regulate curable compositions or strengthens or half strengthen or the compound of increment filler and the supplementary additive used always in the art in respectively for single component or multi-component one or several packings.
- 9. the purposes of claim 8 is characterized in that, is made up of the siloxy units of logical formula V and/or the siloxy units of formula (VI) as the organopolysiloxane of the main component of composition C:In these formulas, each symbol has following meanings:-symbol R is identical or different, represents the group of non-hydrolysable hydrocarbon character separately, and this group is:★ has 1 to 5 carbon atom and comprises the alkyl and the haloalkyl of 1 to 6 chlorine and/or fluorine atom,★ has 3 to 8 carbon atoms and comprises the cycloalkyl and the halogenated cycloalkyl of 1 to 4 chlorine and/or fluorine atom,★ has 6 to 8 carbon atoms and comprises aryl, alkylaryl and the halogenated aryl of 1 to 4 chlorine and/or fluorine atom,★ has the cyano group alkyl of 3 to 4 carbon atoms;-symbols Z is represented hydrogen atom or C separately 2-C 6Thiazolinyl;The integer that-n=equals 0,1,2 or 3;The integer that-x=equals 0,1,2 or 3;The integer that-y=equals 0,1 or 2;The summation of-x+y is 1 to 3.
- 10. the purposes of claim 8, it is characterized in that constituent polyorganosiloxane composition C be known as RTV pass through polyaddition crosslinked at ambient temperature or the single component of heat cross-linking or those compositions of two-pack, it comprises:(a) at least a polydiorganosiloxane of 100 weight parts, being selected from per molecule has at least 2 and is bonded to type homopolymer and the multipolymer that is arranged in the vinyl on chain and/or the terminated Different Silicon atom, its other organic group that is bonded on the Siliciumatom is selected from methyl, ethyl and phenyl, at least 60 moles of % of these other groups are methyl, and it has the average viscosity at 25 ℃ following 200 to 5000mPas;(b) at least a poly-Organhydridosiloxaneresins, be selected from per molecule and on average have at least 2 line style or ring-type homopolymer and multipolymers that are bonded to the hydrogen atom on the Different Silicon atom, its organic group that is bonded on the Siliciumatom is selected from methyl, ethyl and phenyl, at least 60 moles of % of these groups are methyl, and it has the viscosity at 25 ℃ following 5 to 1000mPas, and the consumption of reactant (b) makes that the molar ratio of the hydride functionalities of (b) and vinyl (a) is 1.0 to 10;(c) platinum catalyst of catalytically effective amount;(d) per 100 weight part organopolysiloxane (a)+(b) are combined as the siliceous filler of 0 to 120 weight part.
- 11. the purposes of claim 8, it is characterized in that constituent polyorganosiloxane composition C is those compositions that are known as the single component of passing through the polyaddition heat cross-linking or the two-pack of LSR composition, these compositions are corresponding at as above given definition in claim 10 of the composition that is known as RTV, be the viscosity of vinylated polydiorganosiloxane reactant (a) at this for greater than 1000mPas.
- 12. the purposes of claim 8 is characterized in that constituent polyorganosiloxane composition C is known as the single component of passing through the polyaddition heat cross-linking of poly-addition HCE composition or those compositions of two-pack, it comprises:At least a polydiorganosiloxane glue of (a ') 100 weight parts, it is that per molecule has at least 2 and is bonded to type homopolymer or the multipolymer that is arranged in the vinyl on chain and/or the terminated Different Silicon atom, its other organic group that is bonded on the Siliciumatom is selected from methyl, ethyl, phenyl, at least 60 moles of % of these other groups are methyl, and described glue has under 25 ℃ the viscosity greater than 300000mPas;(b ') at least a poly-Organhydridosiloxaneresins, be selected from per molecule and have at least 3 line style, ring-type or netted homopolymer or multipolymers that are bonded to the hydrogen atom on the Different Silicon atom, its organic group that is bonded on the Siliciumatom is selected from methyl, ethyl, phenyl, at least 60 moles of % of these groups are methyl, and the molar ratio of it has the viscosity at 25 ℃ following 5 to 1000mPas, and the consumption of reactant (b ') makes (b ') the vinyl of hydride functionalities with (a ') is 0.4 to 10;The platinum catalyst of (c ') catalytically effective amount;(d ') per 100 weight part organopolysiloxane (a ')+(b ') are combined as the siliceous filler of 0.5 to 120 weight part.
- 13. the purposes of claim 8 is characterized in that constituent polyorganosiloxane composition C is those compositions that are known as the single component of HCE, it comprises:(at least a polydiorganosiloxane glue of a ") 100 weight parts; it is that per molecule has at least 2 and is bonded to type homopolymer or the multipolymer that is arranged in the vinyl on chain and/or the terminated Different Silicon atom; its other organic group that is bonded on the Siliciumatom is selected from methyl, ethyl, phenyl; at least 60 moles of % of these other groups are methyl, and described glue has under 25 ℃ the viscosity of 300000mPas at least;(the organo-peroxide of b ") 0.1 to 7 weight part;(c ") per 100 weight part glue (a ") be the siliceous filler of 0.5 to 120 weight part.
- 14. each purposes of claim 10 to 13 is characterized in that constituent polyorganosiloxane composition C also comprises one or more supplementary additives (e), is selected from: the product (e1) of at least a what is called " anti-structurizing "; At least a polyorganosiloxane resin (e2); At least a reagent (e3) based on metal oxide or oxyhydroxide or salt; At least aly be used to produce articles colored pigment (e4); At least a boryl compound (e5); The filler of at least a melt type and/or stratiform type (e6), they can with or can not be used in combination under the situation of catching fire, to cause forming the insulating ashy substance with one or more suitable mineral materials; At least a adhesion promotor (e7); Be known as under the situation of passing through the crosslinked silicon composition C of polyaddition of RTV, LSR or poly-addition HCE and at least a crosslinked retarding agent (e8).
- 15. the purposes of claim 1, wherein T 1And T 2The alkyl that is replaced by alkyl is chosen in representative wantonly independently.
- 16. the purposes of claim 1, wherein T 1And T 2The alkyl that is replaced by perfluoroalkyl is chosen in representative wantonly independently.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0502180 | 2005-03-04 | ||
FR0502180A FR2882757B1 (en) | 2005-03-04 | 2005-03-04 | USE OF A PARTICULAR PLATINUM COMPOUND TO IMPROVE THE RESISTANCE OF SILICONE ELASTOMERS AGAINST DEGRADATION BY VERY HIGH TEMPERATURES |
PCT/FR2006/000396 WO2006095068A1 (en) | 2005-03-04 | 2006-02-22 | Use of a specific platinum compound in order to improve the resistance of silicon elastomers to degradation caused by very high temperatures |
Publications (2)
Publication Number | Publication Date |
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CN101133113A CN101133113A (en) | 2008-02-27 |
CN101133113B true CN101133113B (en) | 2011-11-30 |
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CN2006800071161A Expired - Fee Related CN101133113B (en) | 2005-03-04 | 2006-02-22 | Use of a specific platinum compound in order to improve the resistance of silicon elastomers to degradation caused by very high temperatures |
Country Status (8)
Country | Link |
---|---|
US (1) | US8129452B2 (en) |
EP (1) | EP1866364B1 (en) |
JP (1) | JP5367987B2 (en) |
KR (1) | KR20070102730A (en) |
CN (1) | CN101133113B (en) |
ES (1) | ES2387683T3 (en) |
FR (1) | FR2882757B1 (en) |
WO (1) | WO2006095068A1 (en) |
Families Citing this family (4)
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JP5269405B2 (en) * | 2007-12-13 | 2013-08-21 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Flame retardant silicone rubber composition |
CN103649228B (en) * | 2011-07-07 | 2016-01-20 | 蓝星有机硅法国公司 | Carbene in solution is as the purposes of organopolysiloxane polycondensation catalysts |
US20160289416A1 (en) | 2013-06-27 | 2016-10-06 | Bluestar Silicones France Sas | Hot-vulcanisable polyorganosiloxane compositions for use in particular for the production of electrical wires or cables |
CN109970980A (en) * | 2017-12-28 | 2019-07-05 | 埃肯有机硅(上海)有限公司 | One pack system addition type polysiloxane composition |
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US6323253B1 (en) * | 1998-06-01 | 2001-11-27 | Loctite Corporation | Flame-retardant UV and UV/moisture curable silicone compositions |
US6387518B1 (en) * | 1998-12-03 | 2002-05-14 | Wacker-Chemie Gmbh | Silicone rubber compositions for producing cables or profiles with retention of function in the event of fire |
CN1518555A (en) * | 2001-06-07 | 2004-08-04 | ���ǻ�ѧ��˾ | Method for preparing metallic carbene-based catalysts for hyolrosilylation of unsaturated compounds and resulting catalysts |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0816193B2 (en) * | 1985-06-03 | 1996-02-21 | ゼロツクス コ−ポレ−シヨン | Thermally stabilized silicone elastomer |
DE19521757A1 (en) * | 1995-06-14 | 1996-12-19 | Wacker Chemie Gmbh | Porphyrin-containing silicones with increased temperature resistance |
FR2813081B1 (en) * | 2000-08-17 | 2005-12-23 | Rhodia Chimie Sa | PROCESS FOR PREPARING SILICONE OILS BY HYDROSILYLATION OF SYNTHONS CONTAINING AT LEAST ONE HYDROCARBON CYCLE INCLUDING OXYGEN ATOM IN THE PRESENCE OF A CATALYTIC METAL COMPLEX |
FR2825709B1 (en) * | 2001-06-07 | 2005-07-01 | Rhodia Chimie Sa | HYDROSILYLATION ELASTOMER-CROSS-LINKABLE SILICONE COMPOSITION IN THE PRESENCE OF CARBENE-BASED METAL CATALYSTS AND CATALYSTS OF THIS TYPE |
EP1506251B1 (en) * | 2002-05-23 | 2008-10-15 | Rhodia Chimie | Silicone composition which can be crosslinked into an elastomer by hydrosilylation in the presence of carbene-based metal catalysts, and catalysts of this type |
-
2005
- 2005-03-04 FR FR0502180A patent/FR2882757B1/en not_active Expired - Fee Related
-
2006
- 2006-02-22 JP JP2007557529A patent/JP5367987B2/en not_active Expired - Fee Related
- 2006-02-22 CN CN2006800071161A patent/CN101133113B/en not_active Expired - Fee Related
- 2006-02-22 WO PCT/FR2006/000396 patent/WO2006095068A1/en active Application Filing
- 2006-02-22 US US11/817,645 patent/US8129452B2/en active Active
- 2006-02-22 ES ES06725978T patent/ES2387683T3/en active Active
- 2006-02-22 EP EP06725978A patent/EP1866364B1/en active Active
- 2006-02-22 KR KR1020077020236A patent/KR20070102730A/en active Search and Examination
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6323253B1 (en) * | 1998-06-01 | 2001-11-27 | Loctite Corporation | Flame-retardant UV and UV/moisture curable silicone compositions |
US6387518B1 (en) * | 1998-12-03 | 2002-05-14 | Wacker-Chemie Gmbh | Silicone rubber compositions for producing cables or profiles with retention of function in the event of fire |
CN1518555A (en) * | 2001-06-07 | 2004-08-04 | ���ǻ�ѧ��˾ | Method for preparing metallic carbene-based catalysts for hyolrosilylation of unsaturated compounds and resulting catalysts |
Also Published As
Publication number | Publication date |
---|---|
JP2008538220A (en) | 2008-10-16 |
ES2387683T3 (en) | 2012-09-28 |
EP1866364A1 (en) | 2007-12-19 |
EP1866364B1 (en) | 2012-05-16 |
JP5367987B2 (en) | 2013-12-11 |
FR2882757A1 (en) | 2006-09-08 |
FR2882757B1 (en) | 2007-04-20 |
CN101133113A (en) | 2008-02-27 |
WO2006095068A1 (en) | 2006-09-14 |
KR20070102730A (en) | 2007-10-19 |
US20090264563A1 (en) | 2009-10-22 |
US8129452B2 (en) | 2012-03-06 |
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